EP0890621B1 - Coating - Google Patents
Coating Download PDFInfo
- Publication number
- EP0890621B1 EP0890621B1 EP98401622A EP98401622A EP0890621B1 EP 0890621 B1 EP0890621 B1 EP 0890621B1 EP 98401622 A EP98401622 A EP 98401622A EP 98401622 A EP98401622 A EP 98401622A EP 0890621 B1 EP0890621 B1 EP 0890621B1
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- EP
- European Patent Office
- Prior art keywords
- monomers
- latex
- meth
- monomer
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 0 CN[N+]([O-])O*[N+]([O-])=O Chemical compound CN[N+]([O-])O*[N+]([O-])=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the invention relates to processes for preparing latex which lead to surface coatings such as varnish and paints, especially coatings of building materials like bricks, concretes, stones, glasses, metals and plastics. It concerns in particularly latex preparation processes which lead to flexible coatings with low tack and surface tension. She also relates to latices which lead after application and drying to coatings and processes for surface treatment.
- latex aqueous dispersions of polymer particles as obtained by emulsion polymerization.
- hydrophobic polymers such as silicone polymers. But these do not correct the tendency to fouling because they have a low Tg and are oleophylls.
- the problem that the invention seeks to solve therefore consists in placing at the point of preparation processes for coatings meeting the criteria mentioned above.
- the present invention therefore firstly relates to a flexible coating to weak "tack" and low surface tension.
- the flexibility according to the invention is the elongation at break of a film expressed in% and determined according to the protocol described in Example 4.
- the "tack" according to the invention is measured according to a standard internal to the applicant and expressed in J / m 2 .
- the measurement protocol is described in Example 4.
- Hydrophobicity is characterized by the contact angle expressed in degree formed by a drop of water and the film.
- the coating according to the invention Compared to a coating obtained from a reference polymer of same Tg, the coating according to the invention has the same flexibility, a decreased tack and increased hydrophobicity.
- the preferred monomers (B) of the invention are, for B 1, 2-ethyl perfluorooctyl acrylate, hereinafter referred to as AC8, and behenyl acrylate for B 2 .
- the monomers (A) constitute the matrix of the coating and are chosen so that the Tg of the coating remains close to -40 ° C.
- Monomers (B) are chosen for their hydrophobic properties. Amounts of monomers (A) and (B) are defined so that the coating has a sufficient flexibility at the temperature of use. This one depends on obviously from the application. For example, for an external application such that exterior paint for building use temperature is included between -20 and 60 ° C.
- the subject of the present invention is also a latex consisting of a particle dispersion or a mixture of particle dispersions. These dispersions being obtained by emulsion polymerization in an aqueous medium in at least one step of at least one monomer A selected from group I and at least one monomer B selected from group II. Groups I and II are those defined previously.
- the particles in dispersion consist of one or more different polymers.
- the monomer (s) B can (can) be distributed on one or more polymers.
- the totality of (B) is distributed over all polymers of particles in dispersion. This leads to this form when the The polymerization relates to a mixture of monomers containing A and B.
- the invention relates to a method for synthesizing latex.
- This process is based on emulsion polymerization techniques well known to those skilled in the art.
- the reaction is preferably carried out under an inert atmosphere in the presence of radical initiators.
- the initiating system used may be a Red-Ox system such as Na 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 / Na 2 S 2 O 5 , Na 2 SO 3 , a thermal system such as NH4) 2 S 2 O 8 , the amounts used being between 0.2 and 1.0% by weight relative to the total weight of the monomers, preferably between 0.25 and 0.5% by weight.
- the emulsion polymerization reaction according to the invention is carried out a temperature between 65 and 85 ° C and depends on the nature of the Priming system used: 65 - 75 ° C for Red-Ox systems based on peroxodisulfate and metabisulfite, 70 - 85 ° C for thermal systems with base of peroxodisulfate alone.
- the preparation of the latices according to the invention is carried out according to a process of semi-continuous type making it possible to limit the drifts of composition which are function of the differences in reactivity of the different monomers.
- the introduction monomers in the form of a pre-emulsion with part of the water and surfactants is thus generally performed over a period of time of 3 30 hours to 5 hours, it is also useful, although not essential, to make a seeding of 1 to 15% of the monomers.
- Systems emulsifiers used in the emulsion polymerization process according to the invention are selected from the range of emulsifiers having a balance hydrophilic / lipophilic adapted.
- Preferred systems consist of the combination of an anionic surfactant, such as sodium laurysulfate, Nonylphenol ethoxylated sulphates, in particular 20 to 25 moles of oxide ethylene, benzene dodecylsulfonate and ethoxylated sulphated fatty alcohols, and a nonionic surfactant, such as ethoxylated nonylphenols in especially 10 to 40 moles of ethylene oxide and the ethoxylated fatty alcohols.
- anionic surfactant such as sodium laurysulfate, Nonylphenol ethoxylated sulphates, in particular 20 to 25 moles of oxide ethylene, benzene dodecylsulfonate and ethoxylated sulphated fatty alcohols
- a nonionic surfactant such as ethoxylated nonylphenols in especially 10 to 40 moles of ethylene oxide and the ethoxylated fatty alcohols.
- the total amount of emulsifier is generally included in the range from 1 to 5% by weight and preferably from 2 to 4% by weight per compared to the monomers.
- the preparation of the latexes according to the invention is carried out according to a process called "shot" which consists of introducing the monomer B by successive rapid flows and this in order to create the zones rich in B.
- the particles in dispersion according to the invention have an included diameter between 50 and 500 nm.
- Latex as described above can be applied to any support and lead, after drying, to the films or coatings of the invention. They can also be mixed with dyes, mineral fillers or organic compounds or any other additive to formulate a formulation for surface coatings such as paint, varnish, putty, etc ...
- the binders have been synthesized in a conventional manner according to a method of semi-continuous polymerization by simultaneous and separate addition of a solution initiator and a pre-emulsion on a base of the tank, previously heated to 75 ° C, being in the reactor, equipped with a circulation of hot water in the double envelope, a central stirring, and a condenser.
- the latex E is obtained by mixing the latexes A and C in a ratio: 83/17.
- the flexibility of the latexes was evaluated by stretching-elongation 1.6 mm thick films dried 15 days.
- the latexes are demolded after freezer in order to get rid of stickiness and to avoid exercising pre-deformation to products that are very soft at room temperature.
- the measurement of the surface tack was done using the tack probe usually used for PSA (pressure sensitive adhesive).
- PSA pressure sensitive adhesive
- the cylindrical probe ⁇ 5 mm comes into contact with the surface of the polymer for a selected time (from a few seconds to several minutes), then withdraws at a chosen imposed speed (from 0.01 cm / s to 5 cm / s) .
- the force exerted on it by the film is recorded as a function of displacement (cm).
- the measurement of the "tack" J / m 2 ) is given by the calculated energy by integration of the force-displacement curve.
- the hydrophobicity of latexes is quantified by the measurement of the contact angle what does a drop of water do with the surface of the films.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Laminated Bodies (AREA)
Abstract
Description
L'invention concerne les procédés de préparation de latex qui conduisent aux revêtements de surface tels que vernis et peintures, en particulier les revêtements de matériaux de construction comme briques, bétons, pierres, verres, métaux et matières plastiques. Elle concerne en particulier les procédés de préparation de latex qui conduisent aux revêtements flexibles à faibles collant et tension superficiels. Elle concerne aussi les latex qui conduisent après application et séchage aux revêtements ainsi que les procédés pour le traitement de surface.The invention relates to processes for preparing latex which lead to surface coatings such as varnish and paints, especially coatings of building materials like bricks, concretes, stones, glasses, metals and plastics. It concerns in particularly latex preparation processes which lead to flexible coatings with low tack and surface tension. She also relates to latices which lead after application and drying to coatings and processes for surface treatment.
Par latex on entend des dispersions aqueuses de particules de polymères telles qu'elles sont obtenues par polymérisation en émulsion.By latex is meant aqueous dispersions of polymer particles as obtained by emulsion polymerization.
La plupart des latex pour revêtements flexibles sont à base de polymères de basse température de transition vitreuse, désignée par Tg. Les films ou revêtements issus de tels latex présentent, en général, un collant superficiel ou "tack" assez important et donc rédhibitoire pour beaucoup d'applications, en particulier en raison de l'encrassement.Most latexes for flexible coatings are based on polymers of low glass transition temperature, referred to as Tg. films or coatings derived from such latices generally have a tacky superficial or "tack" quite important and therefore prohibitive for many applications, particularly due to fouling.
La solution la plus courante pour réduire le collant, hormis augmenter la Tg en sacrifiant la flexibilité, est de réticuler les films chimiquement ou photochimiquement. Cette solution ne donne pas entière satisfaction.The most common solution to reduce stickiness, apart from increasing the Tg sacrificing flexibility, is to crosslink the films chemically or photochemically. This solution is not entirely satisfactory.
Une autre solution a été décrite par USP 5 308 820. Elle consiste à mélanger une dispersion d'un polymère "dur" apportant le faible collant et une dispersion contenant un polymère "mou" apportant la flexibilité.Another solution has been described by USP 5,308,820. mix a dispersion of a "hard" polymer bringing the low tack and a dispersion containing a "soft" polymer providing flexibility.
Par ailleurs, on peut apporter de l'hydrophobie, ou réduire la tension superficielle des films, par l'ajout de polymères hydrophobes tels que les polymères siliconés. Mais ceux-ci ne corrigent pas la tendance à l'encrassement car ils présentent une basse Tg et sont oléophilles.Moreover, one can bring hydrophobicity, or reduce the tension superficial films, by the addition of hydrophobic polymers such as silicone polymers. But these do not correct the tendency to fouling because they have a low Tg and are oleophylls.
Une autre solution est d'introduire des polymères fluorés comme décrit dans FR 2 725 721.Another solution is to introduce fluoropolymers as described in FR 2,725,721.
DE-A-196 36 490 décrit la production de dispersions aqueuses.DE-A-196 36 490 describes the production of aqueous dispersions.
Il apparait donc difficile, voire impossible, de trouver un revêtement ayant à la fois la flexibilité, l'hydrophobie et le faible collant.It appears difficult, if not impossible, to find a coating having both flexibility, hydrophobicity and low tack.
Le problème que cherche à résoudre l'invention consiste donc en la mise au point de procédés de préparation des revêtements répondant aux critères cités précédemment.The problem that the invention seeks to solve therefore consists in placing at the point of preparation processes for coatings meeting the criteria mentioned above.
Cet objectif a été atteint de manière surprenante à l'aide de dispersions aqueuses de polymères acryliques pouvant être obtenus par polymérisation en émulsion ou suspension d'un ou de plusieurs monomères comprenant des monomères acryliques spéciaux, selon la revendication 1.This goal has been surprisingly achieved by means of dispersions aqueous solutions of acrylic polymers obtainable by polymerization in emulsion or suspension of one or more monomers comprising special acrylic monomers according to claim 1.
Ces latex, appliqués sur un support quelconque, donnent après séchage et formation de film un revêtement flexible et à faible collant et tension superficiels.These latices, applied on any support, give after drying and film forming a flexible coating and low stickiness and tension superficial.
La présente invention a donc d'abord pour objet un revêtement flexible à faible "tack" et à faible tension superficielle. The present invention therefore firstly relates to a flexible coating to weak "tack" and low surface tension.
La flexibilité selon l'invention est l'allongement à la rupture d'un film exprimé en % et déterminé selon le protocole décrit dans l'exemple 4.The flexibility according to the invention is the elongation at break of a film expressed in% and determined according to the protocol described in Example 4.
Le"tack" selon l'invention est mesuré selon une norme interne à la demanderesse et exprimé en J/m2. Le protocole de mesure est décrit dans l'exemple 4.The "tack" according to the invention is measured according to a standard internal to the applicant and expressed in J / m 2 . The measurement protocol is described in Example 4.
L'hydrophobie est caractérisée par l'angle de contact exprimé en degré formé par une goutte d'eau et le film.Hydrophobicity is characterized by the contact angle expressed in degree formed by a drop of water and the film.
Les films de l'invention présentent à la fois :
- une flexibilité supérieure à 1000 % et de préférence supérieure à 1900 %
- un tack inférieur à 95 J/m2 et de préférence inférieur à 85 J/m2 ;
- une hydrophobie exprimée par un angle de contact supérieur à 90° et de préférence compris entre 100 et 120°.
- a flexibility greater than 1000% and preferably greater than 1900%
- a tack of less than 95 J / m 2 and preferably less than 85 J / m 2 ;
- a hydrophobicity expressed by a contact angle greater than 90 ° and preferably between 100 and 120 °.
Comparé à un revêtement obtenu à partir d'un polymère de référence de même Tg, le revêtement selon l'invention présente la même flexibilité, une diminution du tack et une augmentation de l'hydrophobie.Compared to a coating obtained from a reference polymer of same Tg, the coating according to the invention has the same flexibility, a decreased tack and increased hydrophobicity.
Les revêtements obtenus par le procédé de l'invention contiennent :
- de 60 à 99,5 % en poids et de préférence de 70 à 98 % de motifs
issus d'un ou plusieurs monomères (A) choisis dans le groupe I constitué de :
- esters (méth)acryliques tels que le méthacrylate de méthyle, le méthacrylate de butyle, l'acrylate d'éthyl-2-héxyle
- les acides (méth)acryliques
- l'acrylamide et ses dérivés
- les vinyliques
- les styréniques tels que le styrène et ses dérivés.
- from 60 to 99.5% by weight and preferably from 70 to 98% of units derived from one or more monomers (A) chosen from group I consisting of:
- (meth) acrylic esters such as methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate
- (meth) acrylic acids
- acrylamide and its derivatives
- vinyls
- styrenics such as styrene and its derivatives.
Selon une forme avantageuse de l'invention A est l'acrylate d'éthyl-2 héxyle
- de 0,5 à 40 % en poids et de préférence de 2 à 30 % d'un ou de
plusieurs monomères (B) choisi dans le groupe II constitué de :
- monomères perfluorés (B1) répondant à la formule générale : dans laquelle R1 représente un atome d'hydrogène ou un radical alkyl contenant de 1 à 4 atomes de carbone, R2 représente un radical perfluoroalkyl à chaíne linéaire ou ramifiée contenant de 1 à 16 atomes de carbone, X représente un enchaínement bivalent lié à 0 par un atome de carbone et pouvant comporter un ou plusieurs atomes d'oxygène, de soufre et/ou d'azote
- monomères (méth)acryliques (B2) répondant à la formule générale : dans laquelle R3 représente un radical alkyl contenant de 8 à 30 atomes de carbone et de préférence de 18 à 24 atomes de carbone.
- from 0.5 to 40% by weight and preferably from 2 to 30% of one or more monomers (B) chosen from group II consisting of:
- perfluorinated monomers (B 1 ) having the general formula: in which R 1 represents a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms, R 2 represents a perfluoroalkyl radical with a linear or branched chain containing from 1 to 16 carbon atoms, X represents a bivalent sequence linked to 0 by a carbon atom and which may comprise one or more oxygen, sulfur and / or nitrogen atoms
- (meth) acrylic monomers (B 2 ) having the general formula: in which R 3 represents an alkyl radical containing from 8 to 30 carbon atoms and preferably from 18 to 24 carbon atoms.
Les monomères (B) préférés de l'invention sont pour B1 l'acrylate d'éthyl-2 perfluorooctyle, désigné ci-après par AC8 et l'acrylate de béhényle pour B2.The preferred monomers (B) of the invention are, for B 1, 2-ethyl perfluorooctyl acrylate, hereinafter referred to as AC8, and behenyl acrylate for B 2 .
Les monomères (A) constituent la matrice du revêtement et sont choisis de sorte que la Tg du revêtement reste proche de -40°C. Les monomères (B) sont choisis pour leurs propriétés hydrophobantes. Les quantités de monomères (A) et (B) sont définies de manière à ce que le revêtement présente une flexibilité suffisante à la température d'utilisation. Celle-ci dépend bien évidemment de l'application. Par exemple, pour une application externe telle que peinture extérieure pour bâtiment la température d'utilisation est comprise entre -20 et 60°C.The monomers (A) constitute the matrix of the coating and are chosen so that the Tg of the coating remains close to -40 ° C. Monomers (B) are chosen for their hydrophobic properties. Amounts of monomers (A) and (B) are defined so that the coating has a sufficient flexibility at the temperature of use. This one depends on obviously from the application. For example, for an external application such that exterior paint for building use temperature is included between -20 and 60 ° C.
La présente invention a également pour objet un latex consistant en une dispersion de particules ou en un mélange de dispersions de particules. Ces dispersions étant obtenues par la polymérisation en émulsion en milieu aqueux en au moins une étape d'au moins un monomère A choisi dans le groupe I et d'au moins un monomère B choisi dans le groupe II. Les groupes I et II sont ceux définis précédemment.The subject of the present invention is also a latex consisting of a particle dispersion or a mixture of particle dispersions. These dispersions being obtained by emulsion polymerization in an aqueous medium in at least one step of at least one monomer A selected from group I and at least one monomer B selected from group II. Groups I and II are those defined previously.
Les particules en dispersion sont constituées d'un ou de plusieurs polymères différents. Le (les) monomère (s) B peut (peuvent) être réparti (s) sur un ou plusieurs polymères.The particles in dispersion consist of one or more different polymers. The monomer (s) B can (can) be distributed on one or more polymers.
Selon une forme de l'invention la totalité de (B) est répartie sur tous les polymères des particules en dispersion. On aboutit à cette forme lorsque la polymérisation porte sur un mélange de monomères contenant A et B.According to one form of the invention the totality of (B) is distributed over all polymers of particles in dispersion. This leads to this form when the The polymerization relates to a mixture of monomers containing A and B.
Selon une autre forme on peut procéder par étape en mélangeant la dispersion obtenue selon la première forme de l'invention avec au moins une autre dispersion obtenue par la polymérisation d'au moins un monomère A. According to another form, it is possible to proceed step by step by mixing the dispersion obtained according to the first form of the invention with at least one another dispersion obtained by the polymerization of at least one monomer A.
Quelle que soit la forme de l'invention les particules en dispersion contiennent :
- de 60 à 99,5 % en poids et de préférence de 70 à 98 % d'au moins un monomère A choisi dans le groupe I
- de 0,5 à 40 % en poids et de préférence de 2 à 30 % d'au moins un monomère B choisi dans le groupe II.
- from 60 to 99.5% by weight and preferably from 70 to 98% of at least one monomer A chosen from group I
- from 0.5 to 40% by weight and preferably from 2 to 30% of at least one monomer B selected from group II.
L'invention concerne un procédé de synthèse de latex. Ce procédé est basé sur les techniques de polymérisation en émulsion bien connues de l'homme du métier. Ainsi, la réaction est préférentiellement conduite sous atmosphère inerte en présence d'amorceurs radicalaires. Le système d'amorçage utilisé peut être un système Red-Ox tel que Na2S2O8, (NH4)2S2O8 / Na2S2O5, Na2SO3, un système thermique tel que (NH4)2S2O8, les quantités utilisées étant comprises entre 0,2 et 1,0 % en poids par rapport à la masse totale des monomères, préférentiellement entre 0,25 et 0,5 % en poids.The invention relates to a method for synthesizing latex. This process is based on emulsion polymerization techniques well known to those skilled in the art. Thus, the reaction is preferably carried out under an inert atmosphere in the presence of radical initiators. The initiating system used may be a Red-Ox system such as Na 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 / Na 2 S 2 O 5 , Na 2 SO 3 , a thermal system such as NH4) 2 S 2 O 8 , the amounts used being between 0.2 and 1.0% by weight relative to the total weight of the monomers, preferably between 0.25 and 0.5% by weight.
La réaction de polymérisation en émulsion selon l'invention est menée à une température comprise entre 65 et 85°C et est fonction de la nature du système d'amorçage utilisé : 65 - 75°C pour les systèmes Red-Ox à base de peroxodisulfate et de métabisulfite, 70 - 85°C pour les systèmes thermiques à base de peroxodisulfate seul.The emulsion polymerization reaction according to the invention is carried out a temperature between 65 and 85 ° C and depends on the nature of the Priming system used: 65 - 75 ° C for Red-Ox systems based on peroxodisulfate and metabisulfite, 70 - 85 ° C for thermal systems with base of peroxodisulfate alone.
La préparation des latex selon l'invention est effectuée selon un procédé de type semi-continu permettant de limiter les dérives de composition qui sont fonction des différences de réactivité des différents monomères. L'introduction des monomères sous forme d'une préémulsion avec une partie de l'eau et des tensio-actifs est ainsi généralement réalisée sur une période de temps de 3 heures 30 à 5 heures, il est également utile, bien que non indispensable, d'effectuer un ensemencement de 1 à 15 % des monomères. Les systèmes émulsifiants utilisés dans le procédé de polymérisation en émulsion selon l'invention sont choisis dans la gamme des émulsifiants possédant une balance hydrophile/lipophile adaptée. Les systèmes préférés sont constitués par l'association d'un tensio-actif anionique, tel que le laurysulfate de sodium, les nonylphénol sulfates éthoxylés en particulier à 20 - 25 moles d'oxyde d'éthylène, le benzène dodécylsulfonate et les alcools gras éthoxylés sulfates, et d'un tensio-actif non ionique, tel que les nonylphénols éthoxylés en particulier à 10 - 40 moles d'oxyde d'éthylène et les alcools gras éthoxylés.The preparation of the latices according to the invention is carried out according to a process of semi-continuous type making it possible to limit the drifts of composition which are function of the differences in reactivity of the different monomers. The introduction monomers in the form of a pre-emulsion with part of the water and surfactants is thus generally performed over a period of time of 3 30 hours to 5 hours, it is also useful, although not essential, to make a seeding of 1 to 15% of the monomers. Systems emulsifiers used in the emulsion polymerization process according to the invention are selected from the range of emulsifiers having a balance hydrophilic / lipophilic adapted. Preferred systems consist of the combination of an anionic surfactant, such as sodium laurysulfate, Nonylphenol ethoxylated sulphates, in particular 20 to 25 moles of oxide ethylene, benzene dodecylsulfonate and ethoxylated sulphated fatty alcohols, and a nonionic surfactant, such as ethoxylated nonylphenols in especially 10 to 40 moles of ethylene oxide and the ethoxylated fatty alcohols.
La quantité totale d'émulsifiant est généralement comprise dans la gamme de 1 à 5 % en poids et préférentiellement de 2 à 4 % en poids par rapport aux monomères.The total amount of emulsifier is generally included in the range from 1 to 5% by weight and preferably from 2 to 4% by weight per compared to the monomers.
La préparation des latex selon l'invention est effectuée selon un procédé dit "shot" qui consiste à introduire le monomère B par coulées rapides successives et ceci afin de créer les zones riches en B.The preparation of the latexes according to the invention is carried out according to a process called "shot" which consists of introducing the monomer B by successive rapid flows and this in order to create the zones rich in B.
Les particules en dispersion selon l'invention ont un diamètre compris entre 50 et 500 nm.The particles in dispersion according to the invention have an included diameter between 50 and 500 nm.
Les latex tels que décrits précédemment peuvent être appliqués sur tout support et conduire, après séchage, aux films ou revêtements de l'invention. Ils peuvent aussi être mélangés avec des colorants, des charges minérales ou organiques ou tout autre additif pour constituer une formulation pour revêtements de surface tels que peinture, vernis, mastic, etc...Latex as described above can be applied to any support and lead, after drying, to the films or coatings of the invention. They can also be mixed with dyes, mineral fillers or organic compounds or any other additive to formulate a formulation for surface coatings such as paint, varnish, putty, etc ...
Les exemples suivants illustrent l'invention sans la limiter :The following examples illustrate the invention without limiting it:
Les liants ont été synthétisés de manière classique selon un procédé de polymérisation semi continu par addition simultanée et séparée, d'une solution d'amorceur et d'une préémulsion sur un pied de cuve, préalablement chauffé à 75°C, se trouvant dans le réacteur, équipé d'une circulation d'eau chaude dans la double enveloppe, d'une agitation centrale, et d'un condenseur.The binders have been synthesized in a conventional manner according to a method of semi-continuous polymerization by simultaneous and separate addition of a solution initiator and a pre-emulsion on a base of the tank, previously heated to 75 ° C, being in the reactor, equipped with a circulation of hot water in the double envelope, a central stirring, and a condenser.
Certaines synthèses ont été réalisées en milieu tamponné du bicarbonate de sodium ayant été, dans ce cas, introduit dans la préémulsion.Some syntheses were carried out in buffered bicarbonate medium In this case, sodium has been introduced into the preemulsion.
Introduire le pied de cuve dans le réacteur, homogénéiser et porter à 75°C.Introduce the reactor base into the reactor, homogenize and bring to 75 ° C.
Lorsque la termpérature du pied de cuve atteint 75°C, couler la préémulsion et la solution d'amorceur en 4 h.When the temperature of the bottom of the tank reaches 75 ° C, pour the preemulsion and initiator solution in 4 h.
Laisser réagir une heure supplémentaire à 75°C.Allow an additional hour to react at 75 ° C.
Refroidir jusqu'à température ambiante, et filtrer sur toile de 100 microns.Cool to room temperature, and filter on 100 mesh microns.
Identique à l'exemple 1 sauf que le monomère B est introduit par vague successive. Same as Example 1 except that monomer B is introduced by wave successive.
Le latex E est obtenu en mélangeant les latex A et C dans un rapport : 83/17.The latex E is obtained by mixing the latexes A and C in a ratio: 83/17.
Le tableau suivant résume les modes opératoires suivis pour la préparation de différents latex (voir tableau 1).The following table summarizes the procedures followed for the preparation of different latexes (see Table 1).
Tous les latex préparés ont subi les tests suivants :All the prepared latexes have undergone the following tests:
La flexibilité des latex a été évaluée par des tractions-allongement de films de 1.6 mm d'épaisseur séchés 15 jours. Les latex sont démoulés après passage au congélateur de façon à s'affranchir du collant et à éviter d'exercer une pré-déformation aux produits qui sont très mous à température ambiante.The flexibility of the latexes was evaluated by stretching-elongation 1.6 mm thick films dried 15 days. The latexes are demolded after freezer in order to get rid of stickiness and to avoid exercising pre-deformation to products that are very soft at room temperature.
Les éprouvettes sont découpées par l'emporte-pièce ISO 1/2 (polymères Tg = -40°C), la vitesse de traction étant de 200 mm/min.The test pieces are cut by the ISO 1/2 punch (polymers Tg = -40 ° C), the tensile speed being 200 mm / min.
La mesure du collant de surface s'est faite à l'aide de la sonde de tack utilisée habituellement pour les PSA (pressure sensitive adhésive). La sonde de forme cylindrique Ø 5 mm) vient en contact avec la surface du polymère pendant un temps choisi (de quelques secondes à plusieurs minutes), puis se retire à une vitesse imposée choisie (de 0.01 cm/s à 5 cm/s). Au cours du retrait de la sonde la force exercée sur celle-ci par le film est enregistrée en fonction du déplacement (cm). La mesure du "tack" (J/m2) est donnée par l'énergie calculée par intégration de la courbe force-déplacement.The measurement of the surface tack was done using the tack probe usually used for PSA (pressure sensitive adhesive). The cylindrical probe Ø 5 mm) comes into contact with the surface of the polymer for a selected time (from a few seconds to several minutes), then withdraws at a chosen imposed speed (from 0.01 cm / s to 5 cm / s) . During the removal of the probe the force exerted on it by the film is recorded as a function of displacement (cm). The measurement of the "tack" (J / m 2 ) is given by the calculated energy by integration of the force-displacement curve.
L'hydrophobie des latex se quantifie par la mesure de l'angle de contact que fait une goutte d'eau avec la surface des films.The hydrophobicity of latexes is quantified by the measurement of the contact angle what does a drop of water do with the surface of the films.
Les résultats obtenus figurent dans le tableau 2 suivant :
A 0 % AC8 témoin
B 5 % AC8 homogène
C 30 % AC8 homogène
E = A+C 5 % AC8 mélange
At 0% AC8 control
B 5% AC8 homogeneous
C 30% AC8 homogeneous
E = A + C 5% AC8 mixture
Claims (6)
- Method for obtaining a latex by emulsion polymerization, this latex containing polymer particles having a diameter between 50 and 500 nm and comprising:60 to 99.5%, preferably 70 to 98%, by weight of units resulting from one or more monomers (A) chosen from group I consisting of:(meth)acrylic esters, such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl acrylate,(meth)acrylic acids,acrylamide and its derivatives,vinyl monomers andstyrene monomers, such as styrene and its derivatives;0.5 to 40%, preferably 2 to 30%, by weight of one or more monomers (B) chosen from group II consisting of:polyfluorinated monomers (B1) satisfying the general formula: in which R1 represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, R2 represents a perfluoroalkyl radical with a linear or branched chain containing 1 to 16 carbon atoms, X represents a divalent chain unit linked to a 0 via a carbon atom and possibly comprising one or more oxygen, sulphur and/or nitrogen atoms, and
- Method according to Claim 1, characterized in that monomer A is 2-ethylhexyl acrylate.
- Method according to Claim 1 or 2, characterized in that monomer B is 2-ethylperfluorooctyl acrylate or behenyl acrylate.
- Latex containing polymer particles having a diameter of between 50 and 500 nm, obtained by the method according to one of Claims 1 to 3.
- Latex according to Claim 4, which further includes dyes, mineral or organic fillers or any other additive in order to make up a formulation for surface coatings.
- Method for treating a surface by depositing a film thereon, characterized in that a latex according to either of Claims 4 and 5 is applied to the surface.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9708666 | 1997-07-08 | ||
FR9708666 | 1997-07-08 |
Publications (3)
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EP0890621A2 EP0890621A2 (en) | 1999-01-13 |
EP0890621A3 EP0890621A3 (en) | 1999-06-30 |
EP0890621B1 true EP0890621B1 (en) | 2005-12-21 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP98401622A Expired - Lifetime EP0890621B1 (en) | 1997-07-08 | 1998-06-30 | Coating |
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US (1) | US6114045A (en) |
EP (1) | EP0890621B1 (en) |
JP (1) | JPH1171549A (en) |
CN (1) | CN1139643C (en) |
AT (1) | ATE313605T1 (en) |
CA (1) | CA2241325A1 (en) |
DE (1) | DE69832850D1 (en) |
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FR2823757A1 (en) * | 2001-04-23 | 2002-10-25 | Atofina | Scale-inhibiting thermoplastic material useful for making thermally molded articles, especially sanitary ware, comprises copolymer of methyl methacrylate and polyfluoroalkyl (meth)acrylate |
US6660828B2 (en) | 2001-05-14 | 2003-12-09 | Omnova Solutions Inc. | Fluorinated short carbon atom side chain and polar group containing polymer, and flow, or leveling, or wetting agents thereof |
CA2551874A1 (en) * | 2003-12-31 | 2005-07-21 | 3M Innovative Properties Company | Water-and oil-repellent fluoroacrylates |
US7411020B2 (en) * | 2004-12-28 | 2008-08-12 | 3M Innovative Properties Company | Water-based release coating containing fluorochemical |
US20060142530A1 (en) * | 2004-12-28 | 2006-06-29 | Moore George G | Water- and oil-repellent fluorourethanes and fluoroureas |
US7345123B2 (en) * | 2004-12-28 | 2008-03-18 | 3M Innovative Properties Company | Fluoroacrylate-multifunctional acrylate copolymer compositions |
US7291688B2 (en) * | 2004-12-28 | 2007-11-06 | 3M Innovative Properties Company | Fluoroacrylate-mercaptofunctional copolymers |
US7253241B2 (en) * | 2004-12-28 | 2007-08-07 | 3M Innovative Properties Company | Fluorochemical containing low adhesion backsize |
US8722756B2 (en) | 2010-09-01 | 2014-05-13 | Basf Se | Aqueous emulsion polymers, their preparation and use |
JP6076252B2 (en) | 2010-09-01 | 2017-02-08 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Aqueous emulsion polymer, its manufacture and use |
US8907002B2 (en) | 2012-12-20 | 2014-12-09 | Columbia Insurance Company | Coatings for use in high humidity conditions |
CN107672680B (en) * | 2017-09-27 | 2019-10-18 | 阜阳创启工艺品有限公司 | A kind of cargo transport trolley of energy stair climbing |
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BE430402A (en) * | 1937-09-29 | |||
JPS5535042B2 (en) * | 1974-02-28 | 1980-09-11 | ||
JPS5415077B2 (en) * | 1974-02-28 | 1979-06-12 | ||
FR2275721A1 (en) * | 1974-06-19 | 1976-01-16 | Schmenger Mathias | Vibration suppressor in manometer connection line - inlet and return passages of different flow resistance improve response |
JPS5443244A (en) * | 1977-09-13 | 1979-04-05 | Asahi Glass Co Ltd | Moistureproofing and rust prevention of metallic surface |
JPS5529501A (en) * | 1978-08-04 | 1980-03-01 | Daikin Ind Ltd | Water- and oil-repellent copolymer and its use |
JPS60127374A (en) * | 1983-12-15 | 1985-07-08 | Toagosei Chem Ind Co Ltd | Two-pack type composition for water-proofing coating |
JPS63278963A (en) * | 1987-05-11 | 1988-11-16 | Osaka Soda Co Ltd | Coating composition |
JP2693822B2 (en) * | 1988-08-08 | 1997-12-24 | 花王株式会社 | Method for producing fluororesin aqueous dispersion |
JPH02308843A (en) * | 1989-05-25 | 1990-12-21 | Kao Corp | Fluorine-containing resin composition for water-based coating |
JPH04126707A (en) * | 1990-09-14 | 1992-04-27 | N O K Kuriyuubaa Kk | Production of emulsion-type water repelling and oil repelling agent having high flash point |
JPH04277568A (en) * | 1991-03-04 | 1992-10-02 | Kansai Paint Co Ltd | Water-repellent composition and method for water-repellent treatment |
JPH0778154B2 (en) * | 1991-07-11 | 1995-08-23 | ヘキスト合成株式会社 | Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereof |
JPH05140237A (en) * | 1991-11-22 | 1993-06-08 | Mitsui Toatsu Chem Inc | Production of fluoropolymer and its composition |
JP3303327B2 (en) * | 1992-03-18 | 2002-07-22 | 住友化学工業株式会社 | Asymmetric induction catalyst |
JP2660312B2 (en) * | 1992-05-29 | 1997-10-08 | ヘキスト合成株式会社 | Fluorine-containing water- and oil-repellent composition |
JP2698536B2 (en) * | 1992-08-28 | 1998-01-19 | 株式会社日本触媒 | Method for producing aqueous resin dispersion |
JPH06240201A (en) * | 1993-02-18 | 1994-08-30 | Dainippon Ink & Chem Inc | Surface modifier for coating material and coating composition |
ES2237810T3 (en) * | 1993-03-26 | 2005-08-01 | W.L. GORE & ASSOCIATES, INC. | USE IN GARMENTS OF A POLYETRAFLUOROETHYLENE ARTICLE WITH COVERING. |
WO1995001228A1 (en) * | 1993-07-01 | 1995-01-12 | Henkel Corporation | Copolymers useful as printing vehicles |
US5623041A (en) * | 1993-07-01 | 1997-04-22 | Henkel Corporation | Polymers useful as printing vehicles |
DE4340400A1 (en) * | 1993-11-26 | 1995-06-01 | Wacker Chemie Gmbh | Aqueous dispersions of organopolysiloxanes |
JP3346643B2 (en) * | 1994-04-08 | 2002-11-18 | 旭硝子株式会社 | Water-dispersed water / oil repellent composition and method for producing the same |
DE19636490A1 (en) * | 1996-09-09 | 1998-03-12 | Basf Ag | Production of aqueous polymer dispersion for adhesives, binders etc. |
JPH10183049A (en) * | 1996-11-08 | 1998-07-07 | Daikin Ind Ltd | Film-forming composition |
-
1998
- 1998-06-30 DE DE69832850T patent/DE69832850D1/en not_active Expired - Lifetime
- 1998-06-30 AT AT98401622T patent/ATE313605T1/en not_active IP Right Cessation
- 1998-06-30 EP EP98401622A patent/EP0890621B1/en not_active Expired - Lifetime
- 1998-07-07 CA CA002241325A patent/CA2241325A1/en not_active Abandoned
- 1998-07-07 US US09/110,859 patent/US6114045A/en not_active Expired - Fee Related
- 1998-07-08 CN CNB981175929A patent/CN1139643C/en not_active Expired - Fee Related
- 1998-07-08 JP JP10192922A patent/JPH1171549A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0890621A3 (en) | 1999-06-30 |
ATE313605T1 (en) | 2006-01-15 |
EP0890621A2 (en) | 1999-01-13 |
US6114045A (en) | 2000-09-05 |
DE69832850D1 (en) | 2006-01-26 |
CA2241325A1 (en) | 1999-01-08 |
CN1139643C (en) | 2004-02-25 |
CN1212268A (en) | 1999-03-31 |
JPH1171549A (en) | 1999-03-16 |
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